Hydrocarbon conversion process



June l5, 1943. y -w.v l." BEN-Enlcr 2,321,972

HYDROCARBON CONVERSION PRocEss Filed Dec. 5,' 1940.

Patented June 15, 1943 y aszia'zz nrnaocAnnoN colwnasron rnocns Wayne L. Benedict, Chicago, lll.,

versal il Products Company, corporation of Delaware Y asslgnor to yUni- Chicago, lll., aA

Application December 5, i940, sei-iai No. 368,601

s anims. (ci. 19e-52) This application is a continuation-impart of my co-pending application Serial No. 309,716,

filled December 18, 1939.

i This invention relates to an improved method for converting hydrocarbon oils into more valuable hydrocarbons. More specically, it is concerned with a process which involves both thermal and catalytic cracking treatments wherein intermediate conversion products formed in the catalytic cracking treatment are employed as the heat convective medium in supplying heat to the catalytic conversion reaction and in cooling the catalyst undergoing regeneration.

A common practice in the catalytic treatment of hydrocarbons is to employ an extraneous material, such as combustion gases, molten salts, or some other suitable fluid medium, to supply heat to and to conduct heat from the endothermic and exothermic reaction zones, respectively. Generally speaking, however, there are certain disadvantages which accompany an operation employing heat convective media ci the type which have found commercial application. On the one hand, the coefcient of heat ,transfer of the materials and, more specically, combustion gases is relatively low, and on the other hand material, such as molten salts, in most cases, is, relatively speaking, very corrosive, and therefore the materials mentioned either from the standpoint of heat transfer or corrosion render the operation involving the catalytic treatment of hydrocarbons considerably more expensive than a thermal cracking treatment. Liquids, generally speaking, have a higher coeicient of heat transfer than gases. However, due to the relatively high temperature employed in the catalytic reactions, molten salts are the only liquid materials which have found any `great application, largely due to the fact that extremely high temperatures may oe encountered before any decomposition takes place. These materials, therefore, would be the most desirable if it were not for excessive corrosion encountered in the equipment.

In order to obviate the disadvantages inherent in a catalytic cracking process employing heating or cooling media of the types referred to above, but at the same time obtain results comparable with or better than those obtained from systems employing such media, my invention provides for utilizing intermediate products formed in the process in conducting heat from the exothermic reaction zone and conveying heat to the endot'riermic reaction zone.

In the catalytic step of my process two or more reaction zones are employed, the fresh or freshly with at least a portion of said insumciently conregenerated catalyst in one or more zones being used for effecting conversion of the hydrocarbons subjected to contact therewith, while the catalysty in the other zone or zones is undergoing regeneration by contacting therewith oxygen-containing gases which are used in burning from the catalyst carbonaceous substances depositedv thereon. In

. order to effect the desired heating and cooling in the respective reactors, I prefer to cool the exothermic reaction zone by contacting therewith the intermediate conversion products f rom-the catalytic treatment at the desired temperature level and supplying heat to the endothermic reaction zone by contacting therewith the said intermediate conversion products from the exothermic reaction zone. Intermediate conversion products vformed in a catalytic cracking treatment are known to be refractory and capable of withstanding extreme temperatures and pressures with relatively low rates of cracking. These materials may be employed successfully, therefore, as the heat convective medium with little danger of extreme excessive coidng on the external surfaces of the reaction zone. Y

In one specic embodiment the invention comprises fractionating a hydrocarbon oil into light and heavy fractions, subjecting said heavy fraction together with at least a portion of insumciently converted hydrocarbons formed as hereinafter described to a thermal conversion step, subjecting said light fraction together with a portion of insuiliciently converted hydrocarbons formed as hereinafter described to a catalytic conversion step, fractionating the resultant products from each conversion step to separate desired products and insumciently converted hydrocarbons, passing a portion of said insuciently converted hydrocarbons from said catalytic conversion step in indirect heat exchange relationship with said catalytic conversion. step and thereafter supplying them to said thermal `conversion step, subjectingl the remaining portion of said insuilciently converted hydrocarbons from said catalytic conversion step and the aforesaid heavy fraction of the charging oil together verted hydrocarbons from said thermal conversion step to treatment in said thermal conversion step, subjecting a portion of said insuciently converted hydrocarbons from said thermalffconversion step to treatment in said catalytic =con version step, and subjecting another portion of said insumciently converted hydrocarbons rfrom said thermal conversion step to yfurther treatment in said thema] conversion step.

`oil passing therethrough from furnace 2l. y vapors from heating coil 20 are conducted through the reaction zone.

Figure 1 in the accompanying drawing. illustrates diagrammatically in side elevation one specific form of the apparatus which may be employed embodying the broad features of the invention.

Figures 2 and 3 are details of the four-way inlet and outlet valves diagrammatically indicated in Figure l, Figure 2 showing avalve in one position, and Figure 3 showing the passageways therethrough shifted.

Referring now to the drawing, charging oil for the process, which may comprise topped crude oil or any desired fraction thereof, vis introduced through line I, containing valve 2, into pump 3, line l, containing valve 5, into heating coilB, wherein a portion thereof is vaporized and raised to the desired temperature without substantial pyrolytic cracking being eifectedheat being supplied to the oil passing therethrough from furnace 'I. The heated materialfrom heating coil i is conducted through 'line 8, containing valve 9, into fractionator I0, wherein it is fractionated to separate a vaporous light fraction/and a nonvaporous heavy fraction. Said vaporous light fraction is removed through line II, containing l'valve I2, into condenser coil I3 contained in condenser box Il wherein it is condensed, withdrawn through line I5, containingvvalve I6, and commingled in line 16 with the intermediate conversion products formed in the thermal conversion step, as hereinafter described. The mixture, which is preferably of such properties that it is substantially vaporized at conditions employed in catalytic cracking, is introduced into pump I1 and line Il, containingvalve I9, into heating coil 20, wherein it is raised to the desired conversion temperature without substantial pyrolytic cracking being effected, heat being supplied tothe The line 22, containing valve 23, into valve VI, after which the vapors are subjected to treatment in a manner to be described more fully later.

In the particular case here illustrated, two reactors, A and B, are employed and each reactor preferably contains a plurality of relatively small diameter tubes containing catalytic material capable of promoting the desired cracking reaction when in a fresh or freshly regenerated state. In addition, each reactor is preferably equipped with a means for introducing a fluid heating or cooling medium around the tubes for the purpose of supplying heat to, or withdrawing heat from, It is not intended that the invention should be limited in this respect, how- One reactor is at all times employed as a cracking zone while the catalyst in the other reactor is being regenerated by passing therethrough a stream of relatively inert gases (such as. combustion gases, for example) containing controlledamounts vof air or oxygen. The reactors are alternately operated with respect to the service for which they are employed by means of valves VI and V2 through which the reactants and the vregenerating gases are supplied and withdrawn, and by means of valves V3 and V4 through which intermediate conversion products employed asa heating and cooling medium are directed. Any suitable valve arrangement capable of switching the direction of flow of the vstream of reactants and the stream of regenerating gases may be employed within the Scope of the invention, and, for the sake of simplifying the description and illustrating the process without unnecessary complications, each of the switching valves is here illustrated as a single four-way valve in which the position of the two passageways therethrough may be shifted as illustrated in Figures 2 and 3.

Assuming that valves VI, V3, and V4 are each adjusted to the position illustrated in Figure 2 and valve V2 is adjusted to the position illustrated in Figure 3, the hydrocarbon vapors in line 22 pass through Valve VI into line 2l and thence into reactor A where they are contacted with a suitable catalytic material contained therein. While the hydrocarbon vapors are in contact with the catalytic material, the endothermic heat of conversion is supplied to the vapors being converted in the manner to be described more fully later.

'I'he preferred cracking catalysts for use in the present process consist in general of a precipitated alumina hydrogel and/or zirconia hydrogel composited with silica hydrogel, the gel composite being washed, dried, formed into particles, and calcined to produce a catalyst mass. The invention, however, is not limited to these particular catalysts, for other catalysts such as, for example, the hydrosilicates of alumina, acid treated clays, and the like, may be used within the broad scope of the invention.

In the following specification and claims the terms silica-alumina, silica-zirconia, and silica'- alumina-zirconia masses are used in the broad sense to designate the synthetic composites referred to above. The preferred catalysts may be prepared by precipitating silica from a solution as a hydrogel, within or upon which the alumina and/or zirconia is deposited also by precipitation as hydrogels. The silica hydrogel may be prepared conveniently by acidifying an aqueous solution of sodium silicate by the addition of a required amount of hydrochloric acid. After precipitating, the silica gel is preferably washed until substantially free from alkali metal salts. The washed silica hydrogel is then suspended in a solution oi' aluminum and/or zirconium salts and an alkaline precipitant, such as ammonium hydroxide, ammonium carbonate, or `ammonium sulfide, is addedto the solution to precipitate aluminum and/or zirconium hydrogels. The final precipitate, comprising essentially hydrated silica and hydrated alumina and/or zirconia, is washed to substantially completely remove water soluble materials, and dried at about 300 F. to produce a rather crumbly and granular material which may be ground and pelleted or sized to produce sired, toproduce the preferred catalyst.

Cracking temperatures, preferably of the order of 6001000 F. more or less, and pressures ranging, for example, from substantially atmospheric to 200 pounds or more per square inch superatmospheric may be employed when using the preferred catalyst, although the process is not limited to this range of conditions exactly.

While the hydrocarbon conversion reaction is being accomplished in reactor A the catalyst in reactor B may be subjected to regeneration treatment by contacting therewith a suitable inert gas such as combustion gas containing controlled amounts of air or oxygen. Fresh regenerline 49, containing valve atingl gases are introduced to the system through line 18, containing valve 19, by means of which they are conducted to valve VI wherethrough they pass into line 2l' and thence into reactor B.

The carbonaceous substances deposited upon the catalyst in the previous processing period areburned therefrom and the exothermic heat of regeneration is absorbed by the cooling oil introduced, as hereinafter described. Spent re- 'generating gases from reactor B are directed through line 25' to valve V2 wherethrough they pass into line B0, containing valve 8 l, after which the gases may be exhausted or, when desired. the sensible heat from the gases may be recovered in suitable equipment, not shown, and air or oxygen commingled with the resulting cooled gases and the mixture thereafter returned to 'reactor B as the fresh regenerating gases.

The conversion products from reactor A are directed through line 25 into valve V2 wherethey are heated, heat being supplied by furnace 55, to a temperature sufficient to initiate combustion of carbonaceous substances, particularly when the heated intermediate conversion products are brought into contact with the reaction zone in which the catalyst is undergoing regeneration. The heated products leaving heating vcoil 54 are directed through line 56, containing valve 51,.to valve V3, wherethrough they pass into line 58 and thence into reactor B wherein they are contacted with the exterior of the reaction charge, thereby absorbing a substantial portion of the heat produced in the regeneration reaction. The intermediate conversion products,

through they passinto line 26, containing valve i 2l, into fractionator 28. The conversion products supplied to fractionator 28 are fractionated therein to separate vapors boiling substantially in the gasoline range from the higher boiling intermediate conversion products and heavy conversion products, both of which are condensed 4in the fractionating zone.

n The .fractionated vapors separated in fractionator 28 are directed through line 29, con.- taining valve 30, 'to the conventional condenser and receiver, not shown, wherein the normally 'jected to any further treatment. All or the remainder of the heavy conversion products is conducted through line 33, containing valve 3ft. following which it is commingled with the heavy conversion products from the 'thermal' conversion step in line 35, and the resulting mixture is directed through line 35, into pump 37. and line 38, containing valve 39, wherein they are commingled, in line i6, with the non-Vaporous heavy fraction of the charging oil condensed in fractionator IB and withdrawn through line M. containing valve di, into pump i2 and line 38. containing valve QS. This mixture is then directed through line M into heating coil t5 wherein it is heated to the desired conversion temperaturesA which may range, for example. from S50-1000 F. and is preferablymaintained at this tempera- .ture within heating coil @5 for a sufficient period of time to effect substantial thermal cracking,

heat being supplied from furnace 6E. The resultant conversion .products are then withdrawn through line di, containing valve alt, and are commingled in line S3 with the intermediate conversion products from the catalytic conversion step which have been used as the heat exchange medium, as hereinafter described. a

, The intermediate conversion products from the catalytic conversion step, separated and condensed in fractionator 28, are withdrawn through containing valve 53, into heating coil 5d, wherein 50, into pump 5i, line 52,v

leaving reactor B, having a higher heat content than-the entering material are directed through line 59 and valve V4 .wherethrough they pass into line 60, and then through valve V3 into line 6I by means of .which they are introduced to reactor A, wherein they are contacted with the exterior of the reaction zone in which the reactants are undergoing conversion. A portion of the heat contained in the intermediate conversion products is imparted to the reactants undergoing conversion in reactor A, thereby supplying a substantial portion of the heat of conversion thereto. 'Ihe intermediate conversion products leaving reactor A are directed through line 62 Ato valve V4 wherethrough they 'pass int-o line 63,

containing valve 64, and are subsequently commingled with the products from heating coil 45, introduced through line 41, as previously described.

The resulting mixture is conducted through line 63 into reaction chamber 65 which is preferably maintained at substantially the same. or at a slightly reduced, pressure relative ,to that yemployed on the outlet of heating coil 45 and which is preferably insulated to reduce radiation losses therefrom although no insulation appears in the drawing. The resulting conversion products leaving reaction chamber 65 are conducted through line 66, containing valve 6l, into vaporizing and separating chamber 68 which is preferably operated at a reduced pressure relative to that employed on the outlet of reaction chamber 65, which may range, for example, from 50 to 200 pounds or more per square inch. The Vaporous conversion products are separated from the liquid conversion products in chamber 68 and the latter, due to the reduction in pressure, is subjected to substantial further vaporization to form a non-Vaporous liquid residue which is removed from chamber 58 by way of line 69, containing valve 10, cooled and recovered as a product of the process or subjected to any desired further treatment. Vaporous con'. 'ersion products, together with vapors evolved in chamber EB, are conducted through line li,-

containing valve l2, into fractionator 13 wherein they are fractionated to yseparate Vaporous hydrecarbons boiling substantially in the gasoline 'The intermediate conversion products are withdrawn through line 18, containing valve 11, and are thereafter commingled with the light fraction of the charging oil prior to introduction to gthe catalytic conversion step, as previously described. The -heavy conversion products, condensed in-fractionator 13, are withdrawn through line 35, containing valve 36, and are subsequently commingled with a portion of the heavy conversion products formed in the catalytic conversion step, as previously described.

In the catalytic cracking operation, as described above, when the catalyst in reactor A approaches a state of reduced activity, at which time it is advantageous to apply freshly regenerated catalyst for the treatment of the vapors, the supply of air to the regenerating gas stream is momentarily discontinued so that reactor B is purged of oxygen-containing gases, and after the purging in reactor B is completed, valve-Vl is switched to the position in Figure 3 at which time oxygen-free gases are introduced to reactor A and hydrocarbon vapors to reactor B. After a lag corresponding to the time required to drive the vapors from reactor A and the oxygen-free gases from reactor B, valve V2 is switched to the position indicated in Figure 2 at which time oxygen is again admitted tofthe regenerating gas stream.

Either prior to, simultaneously with, or subsequent to the switching of valve Vl and V2, valves V3 and V4 may be switched to the position indicated in Figure 3 in order that the proper heating and cooling may be eected in reactors A and B. After the switching of valves VI, V2, V3, and VI the iiow of hydrocarbon vapors in line 22 will be through valve VI into line 24' and thence to reactor B while the flow of conversion products from reactor B will be through line 25', valve V2, and line 26. 'I'he flow of conversion products from this point on will be substantially as described. The flow of the 'fresh regeneratingy gases, on the other hand, will be through valve Vl into line 24 and thence into reactor A. The spent regenerating gases from reactor A will flow through line 25 to valve V2 and thence into line 80, as previously described. The now of the intermediate conversion products in line 56, employed as a heating and cooling medium to the reaction zones, will be through valve V3 into line 6l and thence into reactor A. 'I'he intermediate conversion products leaving reactor A flow through line 62, valve V4, into line 60, valve V3, into line 58, and thence into reactor B. The intermediate conversion products from reactor B are directed through line 59 and valve V4 into line 63, the flow thereafter being substantially as described.

Switching of the stream of hydrocarbon vapors and regenerating'gases is periodically repeated by reversing the position of the switching valves so that the partially spent catalytic material in one reactor is being continuously regenerated, and the stream of hydrocarbon vapors is being vcontinuously converted in the other reactor. The switching valves may be manually operated but, to simplify operation of the process and to avoid mistakes in the operation of the valves. all of the valves may preferably operate from l. single time cycle controller of any well-known form in accordance with adeiinite predetermined schedule.

An example of one specific operation of the process is approximately as follows, although the invention should not be interpreted as limited exactly in accordance therewith.

Charging oil comprising a v28 A. P. I. gravity -Mid-Continent topped crude was heated and fractionated to produce a light and heavy frac# tion. The light fraction was commingled with the intermediate conversion products from the thermal conversion step formed as hereinafter described, the mixture was heated to a temperature of 950 F. and the resulting vapors subjected to contact with silica-alumina-zirconla catalyst in a reaction zone heated as subsequently described. Simultaneously therewith the catalyst contained in another reaction zone was regenerated by contacting therewith heat regenerating gases containing approximately 2% by volume of oxygen while cooling this zone as subsequently described. The hydrocarbon conversion products from the catalytic reaction step were fractionated to separate gasoline boiling range hydrocarbons, intermediate conversion products, and heavy conversion products. The gasoline produced in this operation amounted to approximately 25% by volume ofthe fresh oil charged. The heavy conversion products, collected and separated as previously described, was commingled with the heavy conversion products from the thermal conversion treatment formed, as hereinafter described, and the mixture was commingled with the heavy fraction obtained by fractionation of the fresh oil charge. The resulting material was subjected to `thermal cracking treatment in a h eating coil and communicating reaction chamber at a temperature of 920 F. and at a superatmospheric pressure of 200 pounds rper square inch on the outlet of the reaction chamber. The intermediate conversion products from the catalytic conversion step were heated to atemperature of 900 F. and contacted first with the exteripr of the reaction zone in which the catalyst was undergoing regeneration to absorb a substantial portion of the heat produced inthe regeneration reaction, after which said mixture was -contacted with the exterior of the reaction zone in which the reactants were undergoing conversion to supply asubstantial portion of the endothermic heat of conversion, following which the mixture was commingled with the products leaving the thermal conversicnheater and the resulting mixture was introduced to the reaction chamber. The mixture of conversion products leavingl the reaction chamber was introduced to a vaporizing and separating chamber wherein the non-vaporous liquid residue, corresponding to approximately 38% by volume of the fresh gas oil, was removed and separated from the vaporous conversion products and the latter was supplied to a fractionating gne to separate gasoline boiling range hydrocarns, heavy conversion products. The gasoline withdrawn amounted to approximately 25% by volume of the fresh charging oil.

I claim as my invention:

1. A conversion process which comprises thermally cracking a relatively heavy hydrocarbon oil, simultaneously subjecting lighter hydrocarbon oil to catalytic cracking in a system comintermediate conversion products, and

eration and then with the catalyst bed being employed in processing and thereafter supplying the same to the thermal cracking operation.

2. The process as defined in claim 1 further characterized in that reflux condensate from the thermal cracking is supplied to the catalytic cracking as at least a part of said lighter oil.

3. A hydrocarbon oil conversion process which comprises fractionating the charging oil to sep- Iarate therefrom a heavy cracking stock and a light cracking stock, thermally cracking said heavy stock and fractionating the resultant vapors, subjecting reilux condensate thus formed and said light stock to catalytic cracking in a system comprising a pair of catalyst beds with each of which the lighting hydrocarbons are alternately contacted, one of the catalystA beds being employed in' processing while the other is undergoing exothermic regeneration, separating from the products of the catalytic cracking a relatively heavy fraction of insufliciently converted f hydrocarbons and a lighter fraction of insufficiently'converted hydrocarbons, supplying at least a portion of said heavy fraction to the thermal cracking operation. passing at least a portion of said lighter fraction in indirect heat exchange relation with the catalyst bed undergoing regeneration and then with the catalyst bed being em-' ployed in processing and thereafter supplying the same to the thermal cracking operation.

WAYNE L. BENEDICT. 

